Ultraviolet absorbing material and ultraviolet absorbing plate

ABSTRACT

An ultraviolet absorbing material prepared by reacting (a) an aminosilane compound of general formula (1) or a derivative thereof wherein R 1  is C 1 -C 10  alkylene or —(CH 2 ) m —NH— (wherein m is an integer of 1 to 4); R 2 3 s are each independently hydrogen, hydroxyl, halogeno, C 1 -C 10  alkyl or C 1 -C 10  alkoxy, with the proviso that at least one of R 2  is C 1 -C 10  alkoxy; and n is an integer of 0 or above with (b) an ultraviolet absorber having a carboxyl group in the molecule in such a way as to form an amide linkage resulting from the above aminosilane compound or derivative thereof. This material can form an ultraviolet absorbing layer and is favorably applicable to ultraviolet-absorbing glass (ultraviolet absorbing plate), optical devices and light modulators.

TECHNICAL FIELD

Generally, there have been employed two methods for providing asubstrate such as a glass sheet with ultraviolet absorbing properties,one of which to coat a substrate with an ultraviolet absorbing materialand the other of which to utilize multi-reflections of a multilayer. Thelatter is excellent in free adjustability of wavelength to be shieldedand capability of clear-cutting, but has a problem relating to cost dueto the complicated production processes. In the former method, there maybe used an inorganic or organic ultraviolet absorber.

Inorganic ultraviolet absorbers as disclosed in Japanese PatentLaid-Open Nos. 5-339033, 5-345639 and 6-56466 are excellent inresistance to weathering and resistance to heat but are disadvantageousbecause these absorbers are less selective because the wavelength ofultraviolet to be absorbed is determined by the band gap of a compoundforming the absorbers and none of these can cut off ultraviolet rays ofwavelengths of neighborhood of 400 nm. Furthermore, most of theabsorbers are involved with unexpected coloration upon interception ofultraviolet rays of longer wavelength.

On the contrary, organic ultraviolet absorbers are broad in range ofabsorptivity and thus can absorb ultraviolet in a wide range ofwavelengths by selecting the type, concentration and thickness of theabsorbers. As a result of extensive research directed to a system havingsuch organic ultraviolet absorbers, it has now been found that use of anabsorber which has a maximum absorption wavelength in a longerwavelength region or which is increased in concentration or in layerthickness is conducive to intercept ultraviolet in a longer wavelengthregion. However, such an absorber having the maximum absorptionwavelength in a longer wavelength region as disclosed in JapaneseLaid-Open Publication No. 6-145387 is poor in resistance to a light andreduced in absorbing power with the lapse of time. This absorber alsohas a problem that the permeability is easily deteriorated due to use ofa fluorescent bleach.

A benzophenic- or benzotriazolic absorber is relatively good inresistance to a light and capable of absorbing ultraviolet rays in arelatively longer wavelength by increasing the concentration and thelayer thickness. However, in the case of coating these absorbers mixedwith a resin over a substrate, the layer formed thereover is limited inthickness to an extent of several tens of micrometers. However, with thelayer of the mixture in this order of thickness, it is necessary to addthe absorbers in a considerably high concentration. Still, the mereaddition of the absorbers in a high concentration leads to problemsinvolving deposition thereof and bleedout due to the use over anextended period of time.

It has been attempted for solving these problems to react an absorberwith a resin in which instance the absorber is copolymerized with anacrylic resin, as disclosed in Japanese Patent Laid Open PublicationNos. 2-248412 and 6-88064. However, since the acrylic resin per se has adrawback in resistance to weathering and heat, the resulting ultravioletabsorber can not bear to be used over a prolonged length of time.Alternatively, various researches have been made on the possibility ofusing an ultraviolet absorber which is reactive a silicone resinexcelled in resistance to weathering and resistance to heat as disclosedin Japanese Patent Laid-Open Publication No. 61-54800, 2-117928 and3-45094. It, however, has been found that most of such absorbers have adifficulty in synthesis in technical view and a problem in durability.

An object of the present invention is to provide an ultravioletabsorbing material which is easy for synthesis and free from bleedout ofthe ultraviolet absorber even after use of a prolonged period of timeand from the foregoing deficiencies even in the case where a longwavelength interception can be achieved in the presence of the absorberin a high concentration. Another object of the present invention is toprovide an ultraviolet absorbing plate which is excellent in resistanceto weathering as well as resistance to heat, free from bleed out afterbeing used for an extended period of time and capable of interceptingultraviolet rays in a longer wavelength region without reducingtransmittance of ultraviolet in a visible region. Disclosure of theInvention

According to the invention, there is provided an ultraviolet absorbingmaterial comprising a reaction product of (a) an aminosilane compound offormula (1) or the derivative thereof with (b) an ultraviolet absorberhaving in its molecules a carboxyl group so as to form amide bondsderived from the aminosilane compound or the derivative thereof,

formula (1) being represented by

 wherein R¹ is a C₁-C₁₀ alkylene group or a divalent group of theformula —(CH₂)m—NH— in which m is an integer of 1-4, R² may be the sameor different and each are selected from the group consisting of ahydrogen atom, a hydroxyl group, a halogen atom, a C₁-C₁₀ alkyl groupand a C₁-C₁₀ alkoxy group provided that at least one of R² is an alkoxygroup, and n is an integer of 0 or greater.

An ultraviolet absorbing plate according to the invention is produced byforming the ultraviolet absorbing layer of an ultraviolet absorbingmaterial having an amide bond and an Si—O bond, on a substrate.

The ultraviolet absorbing material comprises preferably a reactionproduct of (a) an aminosilane compound of formula (1) or the derivativethereof with (b) an ultraviolet absorber having in its molecules acarboxyl group so as to form amide bonds derived from the aminosilanecompound or the derivative thereof,

formula (1) being represented by

 wherein R¹ is a C₁-C₁₀ alkylene group or a divalent group of theformula —(CH₂)m—NH— in which m is an integer of 1-4, R² may be the sameor different and each are selected from the group consisting of ahydrogen atom, a hydroxyl group, a halogen atom, a C₁-C₁₀ alkyl groupand a C₁-C₁₀ alkoxy group provided that at least one of R² is an alkoxygroup, and n is an integer of 0 or greater.

The reaction between the aminosilane compound or the derivative and theultraviolet absorber having in its molecule a carboxyl group ispreferably conducted in the presence of a silicone resin or isconducted, followed by addition of a silicone resin upon completion ofthe reaction.

The ultraviolet absorbing material is preferably produced by reacting(a) an aminosilane compound of formula (1) or the derivative thereofwith (b) an ultraviolet absorber having in its molecules a carboxylgroup in the presence of a silane compound having an epoxy group and/ora colloidal silica so as to form an amide bond derived from theaminosilane compound or by adding a silane compound having an epoxygroup and/or a colloidal silica to a reaction product obtained byreacting (a) an aminosilane compound of formula (1) or the derivativethereof with (b) an ultraviolet absorber having in its molecules acarboxyl group so as to form an amide bond derived from the aminosilanecompound,

formula (1) being represented by

 wherein R¹ is a C₁-C₁₀ alkylene group or a divalent group of theformula —(CH₂)m—NH— in which m is an integer of 1-4, R² may be the sameor different and each are selected from the group consisting of ahydrogen atom, a hydroxyl group, a halogen atom, a C₁-C₁₀ alkyl groupand a C₁-C₁₀ alkoxy group provided that at least one of R² is an alkoxygroup, and n is an integer of 0 or greater.

The substrate is preferably transparent and the ultraviolet absorbinglayer is also preferably transparent.

The substrate preferably comprises a plurality of transparent substrateslaminated one after another and one or more the ultraviolet absorbinglayers interposed therebetween.

An overcoat layer is preferably coated over the ultraviolet absorbinglayer.

The substrate has preferably a transparent electrically conductive layeron the side where the ultraviolet absorbing layer is disposed.

An overcoat layer is preferably disposed between the ultravioletabsorbing layer and the transparent electrically conductive layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view showing one example of theultraviolet absorbing layer according to the invention.

FIG. 2 is a schematic cross-sectional view showing another example ofthe ultraviolet absorbing layer according to the invention.

FIG. 3 is a schematic cross-sectional view showing further anotherexample of the ultraviolet absorbing layer according to the invention.

FIG. 4 is a schematic cross-sectional view showing still another exampleof the ultraviolet absorbing layer according to the invention.

FIG. 5 is a graph showing the visible ultraviolet absorbing spectral ofthe ultraviolet absorbing glass produced in Example 1.

FIG. 6 is a graph showing the visible ultraviolet absorbing spectral ofthe ultraviolet absorbing glass produced in Example 9.

FIG. 7 is a graph showing the visible ultraviolet absorbing spectral ofthe ultraviolet absorbing glass produced in Example 13.

FIG. 8 is a graph showing the visible ultraviolet absorbing spectral ofthe ultraviolet absorbing glass produced in Example 17.

FIG. 9 is a graph showing the visible ultraviolet absorbing spectral ofthe ultraviolet absorbing glass produced in Example 21.

FIG. 10 is a graph showing the visible ultraviolet absorbing spectral ofthe ultraviolet absorbing glass produced in Example 25.

FIG. 11 is a graph showing the visible ultraviolet absorbing spectral ofthe ultraviolet absorbing glass produced in Comparative Example 3.

FIG. 12 is a model graph demonstratively explaining the principle of theway of determining a change rate in ultraviolet absorbing power.

BEST MODE FOR CARRYING OUT THE INVENTION

A substrate used for the present invention may be a transparent oropaque substrate and may be a laminate of these substrates.

There is no particular limitation imposed on the transparent substrate.The transparent substrate may be a colorless or colored glass, a camphorglass, a wire glass, a hot wire reflection glass, a hot wire absorbingglass, a reinforced glass, a glass block or a colorless or coloredtransparent resin. Such transparent glasses may be polyethyleneterephthalate, polyamide, polysulfone, polyethersulfone,polyetherketone, polyphenylene sulfide, polycarbonate, polyimide,polymethylmethacrylate and polystyrene.

The term “transparent” used herein designates visible opticaltransmission ranging from 3-100%, preferably 10-100%. The substrate usedfor the invention has necessarily a smooth surface which may be planneror curved at normal temperature and may be deformable under stress andbe in a vessel-like shape.

There is no particular limitation imposed on the material of the opaquesubstrate. Therefore, eligible materials may be selected from a varietyof glasses such as a soda-lime glass and a borosilicate glass, asynthetic resin, papers, woods, woven textiles, unwoven textiles, knitsand a composite material of two or more of these materials. Eligiblesynthetic resins are polyethylene terephthalate, polyamide, polysulfone,polyether sulfone, polyphenylene sulfide, polycarbonate, polyimide,polymethyl methacrylate and polystyrene. The opaque substrate may bewhite or colored.

The term “opaque” used herein means that visible light can not betransmitted. The opaque substrate used for the present invention hasdesirously an optical transmittance of less than 3%, preferably lessthan 2% at a thickness of 2μm. The opaque substrate used for theinvention has macroscopically a surface, which may not be flat inmicroscopic view and may be curved and deformable under stress.

The ultraviolet absorbing layer has necessarily an amide bondrepresented by (—CONH—) and an Si—O bond. Preferably these bonds areattached to some bonding groups such as (a) a C₁-C₅ alkylene group, (b)a divalent group represented by the formula —(CH₂)m—NH— wherein m is aninteger of 1-4, and (c) a residue derived from (a) or (b).

The contents of the Si—O bond in the ultraviolet absorbing layer shouldbe in an amount of 1-50 mol, preferably 1-30 mol, more preferably 1-15mol per mol of the amide bond.

The ultraviolet absorbing plate comprises preferably an ultravioletabsorbing plate comprising a transparent substrate and an ultravioletabsorbing layer which is less than 40%, preferably less than 30%, morepreferably less than 15% in a change rate in ultraviolet absorbing powerof an ultraviolet after the plate being subjected to 24 hour-extractionin a boiled acetone, which change rate is defined by the followingmathematical formula:

Change Rate in Ultraviolet Absorbing Power (%)=(Absorbance prior toextraction)−(Absorbance after extraction)×100 (Absorbance prior toextraction)

provided that the calculation is carried out using the value ofabsorbance after extraction at an arbitrary wavelength regioncorresponding to that at which absorbance prior to extraction issubstantially 1. Changes in ultraviolet absorbing power can be easilyobserved from an ultraviolet absorbing spectrum. Take for instance, inFIG. 12 there is demonstratively shown the principle of the way ofdetermining change rate in ultraviolet absorbing power and it is cleartherefrom that the wavelength is about 383 nm when the absorbance priorto extraction is 1 and the absorbance after extraction is 0.07 at thesame wavelength. Therefore, the change rate in ultraviolet absorbingpower is calculated to be 93%.

Change in ultraviolet absorbing power results from elusion of acomponent derived from an ultraviolet absorbing compound (usually anorganic ultraviolet absorbing compound) forming an ultraviolet absorbinglayer, into acetone. However, the ultraviolet absorbing component issubstantially free from such elution if it is chemically bonded toanother component in the ultraviolet absorbing layer.

In the case of using an organic ultraviolet absorber having abenzotriazole skeleton or a benzophenon skeleton described hereinafterin details as an ultraviolet absorbing compound, the ultravioletabsorbing layer thus obtained has usually the benzotriazole orbenzophenon skeleton or the structure derived therefrom. However, in thepresent invention, owing to the ultraviolet absorbing compound in theultraviolet absorbing layer bonded through the amide bond to the matrix,the ultraviolet absorbing layer boiled in acetone exhibits no or slightextraction of the structure derived from the ultraviolet absorberthereof. Therefore, the resulting ultraviolet absorbing plate is less inchange rate in ultraviolet absorbing power than the above-specifiedvalues thereby obtaining a very little change rate.

As no particular limitation is imposed on the production method of sucha particular ultraviolet absorbing layer, any suitable methods can beemployed. One of the methods is exemplified as follows:

An aminosilane compound represented by formula (1) given below or thederivative thereof hereinafter referred to as Component A is reactedwith an ultraviolet absorber having in its molecule a carboxyl groupreferred hereinafter to as Component B so as to form an amide bondderived from Component A thereby producing an ultraviolet absorbingmaterial which is coated and cured on a substrate;

formula (1) being represented by

In formula (1), R¹ is a C₁-C₁₀, preferably C₁-C₅ alkylene group or adivalent group of the formula —(CH₂)m—NH— wherein m is an integer of1-4. Such an alkylene group for R¹ may be methylene, ethylene,trimethylene and propylene. R² in formula (1) may be the same ordifferent and each are a hydrogen atom, a hydroxyl group, a C₁-C₁₀,preferably C₁-C₃ alkyl group, a C₁-C₁₀, preferably C₁-C₅ alkoxy groupand a C₆-C₁₀, preferably C₆-C₈ aryl group. At least one of R² ispreferably a C₁-C₅ alkoxy group. Specific examples of the alkyl groupsfor R² are methyl, ethyl, propyl and i-propyl groups. Preferred alkoxygroups for R² are methoxy, ethoxy, propoxy and i-propoxy groups whilepreferred aryl groups are phenyl and tolyl groups. n is an integer ofgreater than 0, preferably between 0 and 3.

Preferred examples of the aminosilane compound of formula (1) are3-aminopropyltriethoxysilane, 3-aminopropyidiisopropylethoxysilane,3-aminopropylmethyldiethoxysilane, 3-aminopropylpolydimethylsiloxane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and3-aminopropyltris(methoxyethoxy)silane. Preferred examples of thederivatives of the aminosilane compound are hydrolysates of the abovepreferred compounds.

These aminosilane compounds and derivatives thereof may be prepared by aconventional method.

Preferred examples of the ultraviolet absorbing material (Component B)having in its molecule a carboxyl group are compounds having one or moreof a carboxyl group at the side chain in the molecule, preferablyorganic compounds and compounds having a benzotriazole skeleton or abenzophenon skeleton.

Preferred compounds having a benzotriazole skeleton are thoserepresented by the formula

In formula (2), R³ is a hydrogen atom, a halogen atom and a C₁-C₁₀,preferably C₁-C₆ alkyl group. The halogen atom for R³ includes fluorine,chlorine, bromine and iodine, while the alkyl group includes methyl,ethyl, propyl, i-propyl, butyl, t-butyl and cyclohexyl groups. R³ issubstituted at the 4- or 5- position of the benzotriazole skeleton,while the halogen atom and the alkyl group are usually located at the4-position. R⁴ is a hydrogen atom or a C₁-C₁₀, preferably C₁-C₆ alkylgroup. Preferred examples of the alkyl group are methyl, ethyl, propyl,i-propyl, butyl, t-butyl and cyclohexyl groups. R⁵ is a C₁-C₁₀,preferably alkylene group or alkylidene group. Preferred examples of thealkylene group are methylene, ethylene, trimethylene and propylenegroups, while preferred alkylidene are ethyliden and propylidene.

Specific examples of the compound of formula (2) are

3-(5-chloro-2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid,

3-(2H-benzotriazole-2-yl)-4hydroxy benzene ethanoic acid and

3-(5-methyl-2H-benzotriazole-2-yl)-5-(1-methylethyl)-4-hydroxybenzenepropanoic acid.

Preferred compounds having the benzophenone skelton arebenzophenone-based compounds represented by the following formulae;

In the formulae, R⁷ and R⁸ may be the same or different and each are ahydroxyl group or a C₁-C₁₀, preferably C₁-C₆ alkyl or alkoxy group. nand m each are an integer ranging from 0 to 3. Specific examples of thealkyl group are methyl, ethyl, propyl, i-propyl, butyl, t-butyl andcyclohexyl groups. Specific examples of the alkoxy group are methoxy,ethoxy, propoxy, i-propoxy and butoxy groups. R⁶ is a C₁-C₁₀, preferablyC₁-C₃ alkylene or alkylidene group. Specific examples of the alkylenegroup are methylene, ethylene, trimethylene and propylene groups.Specific examples of the alkylidene groups are ethylidene andpropylidene groups.

Preferred examples of the compound having the benzophenone skeletoninclude 2-hydroxy-4-methoxybenzophenone-5-carbocylic acid,2,2′-dihydroxy-4-methoxybenzophenone-5-carboxylic acid and4-(2-hydroxybenzoyl)-3-hydroxybenzene propanoic acid.

The ultraviolet absorber having the benzotriazole skeleton or thebenzophenone skeleton may be prepared in a conventional manner.

In the present invention, eligible ultraviolet absorbing material to beformed into an ultraviolet absorbing layer having an amide bond and anSi—O bond onto a substrate includes a component obtained by at leastreacting Component A and Component B so as to form an amide bond derivedfrom Component A. Dehydration is generally employed for the reaction ofComponent A and Component B. No particular limitation is imposed on theamount of the amide bond to be formed. Generally, Components A and B arereacted so that the amide bond is formed in an amount of 100 mol percentof the aminosilane of Component A. However, less than 100 mol percent isstill acceptable. The lower limit is on the order of 50 mol percent.

The inventive ultraviolet absorbing material may contain optionalcomponents in addition to Components A and B to an extent that anaccomplishment of the object of the invention is not hindered. Theoptional components may be added during or after the reaction betweenComponents A and B. Hereinbelow, these optional components are describedin details.

One example of such optional components is exemplified by siliconeresins (hereinafter referred to as Component C). Component C ispreferably a reactive silicone resin having a functional group which isreactive with the alkoxysilyl group of Component A by dehydration and/orremoving an alcohol. Preferred functional groups are an alkoxysilylgroup and a silanol group.

Such a reactive silicone resin can be readily synthesized by subjectingalkoxysilanes or chlorosilanes to partial hydrolysis and thencondensation. Commercially available reactive resins are pure siliconevarnishes as manufactured by Okitsumo Co., Ltd. under the trade name of“X07931-Clear”, silicone resins as manufactured by Tore. Dow-CorningSilicone Co., Ltd. under the trade name of “SR2410” and acrylyl-modifiedsilicone resins as manufactured by Chisso Co., Ltd. under the trade nameof “Sairacoat 1000”. These silicone resins may be put in use in the formof a solution by using a variety of solvents to an extent that anaccomplishment of the objection of the invention does not hindered.Although not restricted, such solvents are a variety ofhydrocarbon-based solvents, ketones, ethers, esters and etheresters.Alternatively, a variety of modified silicone resins are also eligible.

Component C may be co-existed during or after the reaction of ComponentA with Component B, the former being particularly preferred.

Another example of the optional component is a variety of epoxy silanes(hereinafter referred to as Component D) having in their molecule anepoxy group. Preferred epoxy silanes are those represented by thefollowing formulae

In the formulae, R⁹ and R¹¹ may be the same or different and each are aC₁-C₁₀, preferably C₁-C₅ alkylene group or a divalent group representedby the formula —R—O R′— wherein R and R′ each are a C₁-C₁₀, preferablyC₁-C₅ alkylene group, R¹⁰ may be the same or different and each are ahydrogen atom, a hydroxyl group, a C₁-C₁₀, preferably C₁-C₅ alkyl oralkoxy group or a C₆-C₁₀, preferably C₆-C₈ aryl group provided that atleast one of R¹⁰ is an alkoxy group, preferably a C₁-C₅ alkoxy group andn is an integer of greater than 0, preferably between 0 and 3.

Preferred examples of the alkylene group are methylene, trimethylenegroups. Preferred examples of the alkyl group are methyl, ethyl, propyl,i-propyl, butyl, t-butyl, pentyl, hexyl, heptyl and octyl groups.Preferred examples of the alkoxy group are methoxy, ethoxy, propoxy,butoxy, t-butoxy, pentyloxy and hexyloxy groups. Preferred examples ofthe aryl group are phenyl and tolyl groups.

Preferred examples of Component D are

3-glycidoxypropyltrimethoxysilane,

dimethoxy-3-glycidoxypropylmethylsilane,

2-(3,4-epoxycyclohexylethyl)trimethoxysilane,

dimethylethoxy-3-glycidoxypropylsilane,1,3-bis(3-glycidopropyl)-1,3-dimethyl-1,3-dimethoxydisiloxane andmixtures thereof.

Component D may be hydrolyzed before put in use. Alternatively,Component D may be put in use after the epoxy group thereof beingsubjected to ring-open polymerization with use of a suitablepolymerization catalyst. Preferred polymerization catalysts are Lewisacid catalyst such as boron trifluoride, diethylether complex, aluminumchloride and diethyl zinc. No particular limitation is imposed on thering-open polymerization conditions. The polymerization temperature maybe in the range of between −80 and 130° C., preferably −20 and 80° C.and the reaction time may be selected depending upon the conditions andmode of the reaction but usually in the range between 10 minutes and 10hours, preferably 1 hour and 6 hours. Although not restricted, thesolvent used for this reaction may be an aromatic hydrocarbon such astoluene and xylene, ketones and esters.

Although Component D may be co-existed with Components A and B during orafter the reaction therebetween, the latter is preferred. In the case ofusing Component D having the epoxy group having been polymerized to openthe ring thereof, it is preferably added upon the reaction of ComponentsA and B.

Still another example of the optional component is a polyether-modifiedpolysiloxane (hereinafter referred to as Component E) and preferablyrepresented by the formula

In the formula, R¹², R¹³ and R¹⁴ may be the same or different and eachare a C₁-C₁₀, preferably C₁-C₅ alkylene groups, R¹⁵ may be the same ordifferent and each are a hydrogen atom, a hydroxyl group, a C₁-C₁₀,preferably C₁-C₅ alkyl and alkoxy group or a C₆-₁₀, preferably C₆-₈ arylgroup. Preferably at least one of R¹⁵ is a C₁-C₁₀ alkoxy group. m is aninteger of greater than 0, preferably between 1 and 100. n is an integerof greater than 0, preferably between 0 and 10. p is an integer ofgreater than 0, preferably between 0 and 10.

The alkylene group exemplarily includes methylene, trimethylene, andtetramethylene groups. The alkyl group exemplarily includes methyl,ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, hexyl, heptyl and octylgroups. The alkoxy group exemplarily includes methoxy, ethoxy, propoxy,butoxy, t-butoxy, pentyloxy and hexyloxy. The aryl group exemplarilyincludes phenyl and tolyl groups.

Component E of formula (9) exemplarily includestetraethyleneglycol-bis(triethoxysilylethyl)ether,polyethyleneglycol-bis(triethoxysilylethyl)ether,polypropyleneglycol-bis(triethoxysilylethyl)ether and mixtures thereof.Component E may be hydrolyzed before put in use.

Although Component E may be co-existed with Components A and B during orafter the reaction therebetween, the former is preferred.

Particularly, the use of the optional components such as Component D ofepoxysilanes and Component E of polyether-modified polysiloxanes iscontributive to making the resulting ultraviolet absorbing layer toexert excellent performances such as improved adhesivity to a substratewithout marring heat resistance and rigidity even with the thicknessincreased.

The other example of the optional component is an inorganic finedispersion (referred hereinafter to as Component F). Although notrestricted, Component F exemplarily includes dispersions of fineparticles such as silica, alumina, titanium oxide and antimony oxide.

The fine particles are on the order of 1-100 nm in particle size. Thedispersion medium may be water, methanol, xylene and methylethyl ketone.Among commercial products, preferred are “LUDOX” manufactured by Dupontand “XBA-ST” manufactured by Nissan Chemical Co. Ltd.

Although Component F may be co-existed with Components A and B during orafter the reaction therebetween, the former is preferred.

Each of the above-mentioned optional components may be prepared by aconventional method.

The inventive ultraviolet absorbing material to be formed into theabove-specified ultraviolet absorbing layer on a substrate may beprepared by reacting Components A and B solely or in the presence of theabove-described optional components as needed or reacting Components Aand B and thereafter adding the optional components. There is noparticular limitation imposed on the reaction conditions as long as anamide bond derived from Component A is formed. Generally, Component A ismixed with Component B and optionally another component in a solvent,followed by the reaction at a temperature ranging from room temperatureto 350° C., preferably 60 to 250° C., for 5 minutes to 50 hours,preferably 10 minutes to 200 hours. The reaction may be repeated.

The solvent used for this reaction is not restricted as long as it doesnot bother the accomplishment of the purpose of the invention. However,preferred are an aromatic solvent such as toluene and xylene, aketone-based solvent such as cyclohexanone and a mixture thereof.

No particular limitation is imposed on the ratio between Components Aand B upon the reaction. The amount of Component B may be selected fromthe ranges between 5-90, preferably 10-80 mass percent based on thetotal mass of Components A and B.

When the optional components are used for the reaction or added afterthe reaction, no particular limitation is imposed on the amount of eachof the optional components. However, the above-mentioned silicone resin(Component C) may be used in an amount of 5-300, preferably 20-150 masspercent based on the total mass of Components A and B. Theabove-mentioned epoxysilanes (Component D) may be used in an amount of10-500, preferably 100-400 mass percent based on the total mass ofComponents A and B. The above-mentioned polyehter-modified polysiloxanes(Component E) may be used in an amount of 100-500, more preferably100-400 mass percent based on the total mass of Components A and B. Theabove-mentioned inorganic fine particles dispersions may be used in anamount of 5-400, preferably 10-200 mass percent based on the total massof Components A and B.

The ultraviolet absorbing material thus obtained may be applied on asubstrate as a coating component immediately after completion of theabove-described reaction or after being added with the optionalcomponents. Alternatively, the resulting coating component may be coatedafter being added with another variety of optional components.

Such components exemplarily include various types of antioxidants, aquencher, a free-radical capturing agent, an inorganic or organic acidsuch as hydrochloric acid, sulfuric acid and acetic acid, a Lewis acidsuch as a boron trifluoride, diethylether complex and sodium antimonyacid hexafluoride, a base such as potassium hydroxide, sodium hydroxide,triethylamine and aniline, a catalyst having a curing accelerationeffect (to be preferably used in an amount of 0.1-5.0 mass percent basedon the ultraviolet absorbing material) such as an organic metalincluding dibutyltin dilaurate and titanium tetraiso propoxide and asolvent such as toluene, xylene, ethanol, isopropanol, thinner,dimethylformamide, cyclohexane and 1-methoxy-2-acetoxypropane.

The inventive ultraviolet absorbing layer may be formed by coating theultraviolet absorbing material on a substrate and then curing the same.

The ultraviolet absorbing material prior to be coated is usually in aliquid state. Therefore, any suitable conventional coating methods maybe employed such as spin coating, spray coating, cast coating, bladecoating, dip coating and flow coating.

The curing reaction may be conducted at a temperature between roomtemperature and 250° C., preferably 60 and 250° C. if using theaforementioned catalyst having an acceleration effect. Without thecatalyst, the ultraviolet absorbing material can be cured at atemperature between room temperature and 350° C., preferably 60 and 250°C. The curing reaction may be carried out usually for 10 minutes to 5hours.

Although not restricted, the ultraviolet absorbing layer formed on asubstrate may have a thickness in the range of usually 0.5-50 μm. Lessthan 0.5 μm would fail to attain a suffice ultraviolet shielding effect,while greater than 50 μm would lead to a difficulty in coating due tocracking.

By the methods and components as described above, there can be producedan ultraviolet absorbing plate comprising an ultraviolet absorbing layerhaving an Si—O bond and formed on a substrate.

The ultraviolet absorbing plate according to the invention is capable ofshielding almost completely or completely transmitting lights in anultraviolet region of 300-400 nm. More specifically, the ultravioletabsorbing plate can shield more than 95% of transmitting lights in theultraviolet region. More over, more than 98% and more than 99% oftransmitting lights in an ultraviolet region can be shielded with apreferred embodiment and more preferred embodiment of the inventiveultraviolet absorbing plate, respectively.

In the present invention, the ultraviolet absorbing layer issubstantially transparent and preferably is almost or completely freefrom a reduction in transmission in visible light ranges peculiar to asubstrate at all. The final ultraviolet absorbing plate is preferablytransparent.

The inventive ultraviolet absorbing plate comprises at least a substrateand an ultraviolet absorbing layer but may have an overcoat layer overthe ultraviolet absorbing layer thereby providing functions such asresistance to wear and chemicals.

Although not restricted, preferred materials for the overcoat layer areresins excelled in resistance to heat. Specific examples of such resinsinclude a silicone resin such as polyimide, polyamide, polycarbonate,polyarylate, polyethersulfone, melamine resin, phenol resin, epoxy resinand silicone varnish and a urea resin, among which the silicone resinsare particularly preferred. These may be used in combination with aglass filler or an inorganic powdery material. Eligible inorganicpowdery materials are powders of ZnO, TiO₂, CeO₂ or silica. Eligiblesilicone resins are those having inorganic fine particles such ascolloidal silica dispersed therein, partially hydrolyzed products orpartially condensed products of silanes such as alkoxysilane andchlorosilane. Specific examples of the silicone silane which arecommercially available are “Tossguard 510” manufactured by TohsibaSilicone, “APZ7703” and “APZ7705” manufactured by Nihon Unicar andpolysllazane manufactured by Tohnen under the trade name of N-L110 andN-L710. A partially hydrolyzed product of epoxysilane is also known as asuitable overcoat material which is excelled in resistance to wear.Although not restricted to the method for forming the overcoat layer andthus an suitable method can be employed, the overcoat layer is generallyformed by coating a solution of the resins or the precursor thereof.After coating, a suitable treatment may be applied slectively dependingupon the nature of the resin. Alternatively, an overcoat layer can beformed by applying a film of the above-described resin.

For example, a silicone varnish is added with a catalyst such asdibutyltin dilaurate and coated over the ultraviolet absorbing layer,followed by heat-curing at a temperature of 100-200° C. for 5 minutes to2 hours thereby obtaining an overcoat layer having a thickness of 1-20μm. Alternatively, if using an acryl-melamine resin precursor, it iscoated and then cured at a temperature of 130-190° C. for 5 minutes to 2hours thereby obtaining an overcoat layer having a thickness of 10-100μm. Further alternatively, if using a photo-curable type acryl basedresin precursor, it is coated and then placed under irradiation from ahigh-tension mercury vapor lamp thereby obtaining an overcoat layerhaving a thickness of 1-10 μm within 5 minutes.

The coating may be conducted by a known method for which instance spincoating, spray coating, blade coating and dip coating. Alternatively,prior to forming an overcoat layer, the coatability and adhesivity to anultraviolet absorbing layer can be improved by optical surfacemodification and primary coating treatments.

The inventive ultraviolet absorbing plate may have over the overcoatlayer a film of metal oxides possessing heat wave reflection andinsulating functions. The film can be formed by a sputtering method or asolgel method thereby providing the ultraviolet absorbing plate withfunctions such as heat wave reflection and insulation.

The inventive ultraviolet absorbing plate is characterized by itscapability of shielding ultraviolet rays in longer wavelength regions,compared with conventional ones. Although not restricted, the inventiveultraviolet absorbing plate can be applied to an ultravioletinterceptive glass, a multilayered glass, a laminated glass, a heat wavereflective and ultraviolet interceptive glass, a heat wave andultraviolet absorbing glass and an anti-fogging ultraviolet absorbingglass for windows of houses, a shopwindow, a functional glass forautomobiles, vehicles, airplanes and ships, an ultraviolet interceptivefilm having the above-described ultraviolet absorbing layer formed on afilm made from a resin and a film for agricultural use and for agreenhouse. Furthermore, the inventive ultraviolet absorbing plate maybe those obtained by forming the above-described ultraviolet absorbinglayer directly on the following articles instead of the above-describedsubstrate. The articles can be exemplified by showcases, specimen cases,bulletin boards, architraves, glasses, sun glasses, cathode-ray tubes,LCD (Liquid Crystal Display) such as TN (Twisted Nematic), STN(Supertwisted Nematic), DSTN (Dual-scanned Supertwisted Nematic), FSTN(Film-compensated Supertwisted Nematic), OMI (Optical ModeInterference), ROCB (Reflective Optical Mode Interference), BTN(Bystable Twisted Nematic), ECB (Electrically Controlled By- fleegence),PALC (Plasma Addressed Liquid Crystal), G/H (Guest Host), mixed mode,PDLC (Polymer Dispersed Liquid Crystal), IPS (In Plane Switching), FLC(Ferroelectric Liquid Crystal) and AFLC (Anti-ferroelectric LiquidDisplay), PDP (Plasma Display Panel), FED (Field Emission Display),light-emission diode, thermochromic, electrochromic and photochromicdevices, electroluminescence devices, light fittings, bottles andplastic containers for foods, soft drinks, liquors and cosmetics andplastic molded articles and so on.

Furthermore, the inventive ultraviolet absorbing plate can be used asvarious types of optical filters which are disposed on the outer orinner side of the above-mentioned devices or elements to provide it withultraviolet absorbing capability. The inventive ultraviolet absorbingplate may be modified to the filter by providing the above-describedultraviolet absorbing layer directly on a substrate for various types ofLCD, an elctrochromic device, a photochromic device, a PDP device, anFED device, a light-emitting diode, a thermochromic device and anelctroluminscence device and a substrate made of a transparent glass ora transparent plastic film. These optical filters may be suitablydisposed anywhere in the above-mentioned devices.

In the case where the inventive ultraviolet absorbing plate is in theform of a multi-layer constituted by two or more of transparentsubstrates and having necessarily an ultraviolet absorbing transparentplate obtained by forming an ultraviolet absorbing layer on atransparent substrate, the embodiments of such multi-layer type plateare selective depending on the purpose thereof. The combinations oftransparent substrates are illustrated as follows:

(1) an ultraviolet absorbing transparent plate and a transparent platehaving no ultraviolet transparent layer (transparent substrate),

(2) two ultraviolet absorbing transparent plates,

(3) an ultraviolet absorbing transparent plate and a heat wavereflective transparent plate,

(4) an ultraviolet absorbing transparent plate and an ultravioletreflective transparent plate,

(5) an ultraviolet absorbing transparent plate, a non-ultravioletabsorbing transparent plate and a heat wave reflective transparentplate,

(6) an ultraviolet absorbing transparent plate and a selected wavelengthreflective transparent plate, and

(7) an ultraviolet absorbing transparent plate and a low emissivitytransparent plate.

Needless to mention, the material of each transparent substrate may bethe same or different. In the case of using an ultraviolet absorbingtransparent plate, the ultraviolet absorbing layer formed thereon may beexposed to the outside or built in when assembled into the multiplelayer plate, the latter being preferred.

These transparent plates may be contacted to each other or contacted soas to have a functional material intervened therebetween. Furthermore,the transparent plates may be disposed with a space to be vacuumed orfilled with dry air, an inactivate gas or a functional material.

The ultraviolet absorbing multi-layered plate may be prepared by a knownmethod except using at least one ultraviolet absorbing transparentplate. Specific examples of the multi-layered plate are as follows. Forexample, a multi-layered glass can be easily produced by using a spacer,a corner key, a drying agent, a sealer and a sealant in a suitablecombination, the materials of which are not limited. For example, thespacers may be those of metals such as aluminum and alloy or of resinssuch as vinyl chloride. The corner keys used in combination with thespacer may be those of metals or resins. The drying agents to be putinto the spacer are porous materials such as silica gel and zeolite. Asa primary sealant, there may be used a polyisobutylene sealantcontaining butyl rubber as a main component. As a secondary sealant,there may be a polysulfide sealant. In the case of a laminated glass,there may be used a polyvinylbutyral resin and a polyurethane resinethylene-vinyl acetate copolymer. In order to improve resistance topenetration, a resin film of polycarbonate or polyester may be insertedbetween interlayers each disposed on the confronting surfaces of twoglasses.

In the case where the inventive ultraviolet absorbing plate is anultraviolet absorbing electrically conductive transparent which isproduced by forming the ultraviolet absorbing layer on a transparentsubstrate having a transparent electrically conductive layer thereon,the above-described overcoat layer may be disposed between theultraviolet absorbing layer and the transparent electrically conductivelayer.

No particular limitation imposed on the transparent electricallyconductive layer employed for the present invention as long as itsatisfies the requirement for transparency. For example, there may beused thin films of metal such as gold and silver and metal oxides suchas ITO (In₂O₃—SnO₂), tin oxide, zinc oxide and vanadium oxide.

The film thickness is usually 100 to 5000 Å and preferably 500 to 3000Å. The surface resistance (resistivity), which may be selected to asuitable value depending upon the usage of the transparent electricallyconductive plate, is usually 0.5 to 500 Ω/cm², preferably 2 to 50 Ω/cm².

There is no particular limitation imposed on the method for forming thetransparent electrically conductive layer and thus any of known methodsmay be employed depending upon the types of the metal oxides and metalsused for the electrically conductive layer. Such methods may beexemplified by a vacuum deposition method, an ion plating method, asputtering method and a solgel method. In any of these methods, theelectrically conductive layer may be formed at the transparent substratetemperature ranging from 100° C. to 350° C.

The ultraviolet absorbing transparent electrically conductive substratehas preferably the above-specified specified ultraviolet absorbing layerbetween the transparent substrate and the transparent electricallyconductive layer. The overcoat layer may or may not be disposed betweenthe ultraviolet absorbing layer and the transparent electricallyconductive layer. The simplest structure of the ultraviolet absorbingtransparent electrically conductive substrate according to the inventionhas a transparent substrate 11, an ultraviolet absorbing layer 12, anovercoat layer 13 and a transparent electrically conductive layer 14, inthis order, as shown in FIG. 1.

One or more intermediate layers 15 may also be provided between thetransparent substrate 11 and the ultraviolet absorbing layer 12 as shownFIG. 2. Although there is no limitation to the function of theintermediate layer 5, it may be an ultraviolet absorbing layercontaining inorganic oxides such as ZnO, CeO₂, and TiO₂ so as tosuppressing deterioration of the organic ultraviolet absorber by farultraviolet rays. Alternatively, the intermediate layer containing asilane coupling agent or a surfactant may also be provided for improvingadhesion between the transparent substrate 11 and the ultravioletabsorbing layer 12.

Furthermore, one more intermediate layers may be provided between theultraviolet absorbing layer 12 and the overcoat layer 13 as shown 3. Nolimitation is imposed on the functions of the intermediate layer 16. Forexample, an intermediate layer containing silane coupling agents orsurfactants may be provided for improving adhesion between the overcoatlayer 13 and the transparent electrically conductive layer 14.

More over, one or more intermediate layer 15, 16 may also be providedbetween the transparent substrate 11 and the ultraviolet absorbing layer12 and between the overcoat layer 13 and the ultraviolet absorbing layer12, respectively as shown in FIG. 4. Although there is no limitation tothe functions of the intermediate layers 15, 16, they may have thefunctions similar to those explained with FIGS. 2 and 3.

The above-described layers may be provided not only on one surface butalso both surfaces of the transparent electrically conductive plate.

Industrial Utility of the Invention

As described above, the ultraviolet absorbing material according to theinvention has superior ultraviolet shielding effect and thus can be usedas a suitable coating material which can easily provide weatheringresistance and heat resistance properties. Due to the amide bond betweenthe ultraviolet absorber and the matrix, the inventive ultravioletabsorbing material is free from bleedout and can maintain excellentultraviolet absorbing power even over an extended period of time.Therefore, the ultraviolet absorbing plate according to the inventionhas an amide bond and an Si—O bond in its ultraviolet absorbing layerand can maintain excellent durability even with the high concentrationof the ultraviolet absorbing components. In addition, the inventiveultraviolet absorbing plate is superior in resistance to weathering andresistance to heat and can sharply shield ultraviolet rays of longerwavelength with transmittance in visible regions being hardly reduced.The inventive ultraviolet absorbing plate has thus an extremely superiorresistance to deterioration by ultraviolet rays and can be used as avariety of materials and products required to have a long duration oflife.

In the case of the inventive ultraviolet absorbing plate comprising atransparent electrically conductive substrate, it has high electricalconductivity and superior ultraviolet shielding effect. In particular,if the ultraviolet absorbing layer is suitably selected, wavelength of400 nm or less can be shielded very sharply. In addition, since thetransparent electrically conductive layer can be formed easily due tothe effect obtained by the overcoat layer interposed between thetransparent electrically conductive layer and the ultraviolet absorbinglayer, it becomes possible to protect an electric device produced byusing the transparent electrically conductive layer against ultravioletrays. By the chemical bond of the ultraviolet absorber to a polymer, theresulting ultraviolet absorbing layer is stable even during formation ofthe transparent electrically conductive layer, allowing to produce thetransparent electrically conductive plate having the ultravioletabsorbing layer with ease. Because of the above features of thetransparent electrically conductive substrate, it is highly useful as anelectrochromic element aimed at light transmission control and displayand a liquid crystal element for display.

The present invention will be further described by way of the followingexamples, which however should not be constructed in a limiting sense.In the examples, the measurements of ultraviolet absorbance and lighttransmittance to derive a change rate in ultraviolet absorbing power wasconducted by using a device manufactured by Hitachi Seisaku-sho Co.,Ltd. under a trade name U-3300 type spectrophotometer, in a wave rangeof 300 to 500 nm.

EXAMPLE 1

Synthesis of Ultraviolet Absorbing Layer Having Carboxyl Group

225 grams (0.46 mol) of octyl3-(5-chloro-2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenpropanate manufactured by Chiba-Geigy Co., Ltd. under the trade name ofTINUVIN 109 were dissolved in 700 ml acetone and then added with 600 ml2N sodium hydroxide solution, followed by stirring at room temperaturefor 24 hours. The resulting mixture was acidified with 650 ml 2Nhydrochloric acid and filtered to obtain an insoluble product, followedby washing it with distilled water until the filtrate being neutralized.The resulting product was dried in vacuum and recrystalized in toluenethereby obtaining 3-(5-chloro-2H-benzotriazole-2-yl)-5-(1,1-dimethylehtyl)-4-hydroxyy-benzene propanoic acid referred to asCompound A hereinafter.

Preparation of Ultraviolet Absorbing Material

3 grams of 3-aminopropyltriethoxysilane were dissolved in 35 grams ofxylene and added gradually with 5 grams of Compound A while being heatedat a temperature of 80° C. Upon completion of the addition, theresulting mixture was heated up to a temperature of 130° C. and refluxedfor 3 hours. The mixture was disposed still to cool down and added with16 grams 3-glycidopropyltrimethoxysilane thereby obtaining anultraviolet absorbing material (coating liquid).

¹³C-NMR analysis of the resulting ultraviolet absorbing materialrevealed that there was a peak of carbonyl at about 173 ppm therebyconfirming the existence of an amide bond derived from the aminosilanecompound.

Preparation of Ultraviolet Absorbing Plate

The ultraviolet absorbing material obtained above was spray-coated overa glass substrate and disposed still at room temperature for 20 minutesthereby obtaining an ultraviolet absorbing glass (ultraviolet absorbingplate) having an ultraviolet absorbing layer of 17 μm thickness.

A portion of the ultraviolet absorbing layer was scraped out andsubjected to ¹³C-NMR analysis. It was observed that there was a peak ofcarbonyl (about 173 ppm) derived from the amide bond. ²⁹Si-NMR analysisalso revealed the existence of the Si—O bond.

FIG. 5 shows ultraviolet visible absorbing spectrum of the ultravioletabsorbing glass. As apparent from FIG. 5, this glass fully shieldedultraviolets of less than 400 nm. Furthermore, this glass performed asuperior ultraviolet shielding effect over an extended period of time.

EXAMPLE 2

Preparation of Ultraviolet Absorbing Multi-layer Glass

A multi-layer glass was prepared in a conventional manner by using theultraviolet absorbing glass obtained in Example 1 and a commercial sodalime glass. There were used an aluminum spacer, a corner key, a butylrubber, a drying agent and polysulfide all of which are manufactured byTeipa Chemical Industry Co., Ltd. The resulting multi-layer glass wassuperior in heat resistance and capable of perfectly shieldingultraviolets over an extended period of time.

EXAMPLE 3

A silicone resin (APZ-7705, manufactured by Nippon Unicar Co., Ltd.) wasspray-coated over the ultraviolet absorbing layer of the ultravioletabsorbing glass obtained in Example 1 and dried at a temperature of 100°C. for 20 minutes thereby forming a protection layer having a thicknessof 2 μm.

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the protection layer by sputtering at a substratetemperature of 250° C. to form a transparent electrically conductivelayer having a layer thickness of about 3300 Å and an electricalresistance of 7.5 Ω/cm² thereby producing a transparent electricallyconductive substrate having ultraviolet absorbing capability. FIG. 5shows the spectral transmittance of the transparent electricallyconductive substrate.

EXAMPLE 4

The ultraviolet absorbing material obtained in Example 1 wasspray-coated over a stainless plate of red color and disposed still for20 minutes, followed by heating at a temperature of 200° C. for 20minutes thereby obtaining an ultraviolet absorbing resin plate having anultraviolet absorbing layer with a thickness of 17 μm. The resultingresin plate was left under radiation of ultraviolet ray and observed tobe extremely less in discoloration than a plate devoid of the coating.

EXAMPLE 5

Preparation of Ultraviolet Absorbing Material

3 grams of 3-aminopropyltriethoxysilane were dissolved with 40 grams ofxylene and gradually added with 5 gram Compound A prepared in Example 1while being heated at a temperature of 60° C. After completion of theaddition, the mixture was heated up to a temperature of 130° C. andrefluxed for 3 hours thereby obtaining an ultraviolet absorbing materialin the form of a solution.

A peak of carbonyl at about 173 ppm derived from the amide bond wasobserved by ¹³C-NMR analysis of the resulting solution therebyconfirming the existence of the amide bond derived from the aminosilanecompound.

Preparation of Ultraviolet Absorbing Plate

The ultraviolet absorbing material was spray-coated over a glass plateand disposed still at room temperature for 20 minutes, followed byheating at a temperature of 130° C. for 30 minutes thereby producing anultraviolet absorbing glass (ultraviolet absorbing plate) having anultraviolet absorbing layer with a thickness of 10 μm.

A portion of the ultraviolet absorbing layer was scraped out andsubjected to ¹³C-NMR analysis. It was observed that there was a peak ofcarbonyl (about 173 ppm) derived from the amide bond. ²⁹Si-NMR analysisalso revealed the existence of the Si—O bond.

The ultraviolet absorbing spectrum of the ultraviolet absorbing glasswas measured and found to perfectly shield ultraviolets similarly tothat of Example 1. Furthermore, this glass performed a superiorultraviolet shielding effect over an extended period of time.

EXAMPLE 6

Preparation of Ultraviolet Absorbing Multi-layer Glass

A multi-layer glass was prepared in a conventional manner by using theultraviolet absorbing glass obtained in Example 5 and a commercial sodalime glass. There were used an aluminum spacer, a corner key, a butylrubber, a drying agent and polysulfide all of which are manufactured byTeipa Chemical Industry Co., Ltd. The resulting multi-layer glass wassuperior in heat resistance and capable of perfectly shieldingultraviolets over an extended period of time.

EXAMPLE 7

A silicone resin (APZ-7705, manufactured by Nippon Unicar Co., Ltd.) wasspray-coated over the ultraviolet absorbing layer of the ultravioletabsorbing glass obtained in Example 5 and dried at a temperature of 100°C. for 20 minutes thereby forming a protection layer having a thicknessof 2 μm.

The ultraviolet visible absorbing spectrum of the ultraviolet absorbingglass having a protection layer thus formed was measured and found toshield completely ultraviolet similarly to that of Example 5.

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the protection layer by sputtering at a substratetemperature of 250° C. to form a transparent electrically conductivelayer having a layer thickness of about 3300 Å and an electricalresistance of 7.5 Ω/cm² thereby producing a transparent electricallyconductive substrate having ultraviolet absorbing capability. Similarlyto Example 5, the substrate exhibits little change in spectrum, comparedwith that before sputtering.

EXAMPLE 8

The ultraviolet absorbing material obtained in Example 5 wasspray-coated over a red polyethylene terephthalate (TET) of red colorand disposed still for 20 minutes, followed by heating at a temperatureof 200° C. for 20 minutes thereby obtaining an ultraviolet absorbingresin plate having an ultraviolet absorbing layer with a thickness of 17μm. The resulting resin plate was left under radiation of ultravioletray and found to be extremely less in discoloration than a plate devoidof the coating.

EXAMPLE 9

Preparation of Ultraviolet Absorbing Material

17.7 grams of silicone varnish manufactured by Okitsumo Co., Ltd. underthe trade name of XO-7931-CLEAR and 3 grams of3-aminopropyltriethoxysilane were dissolved in 35 grams of xylene andadded gradually with 5 grams of Compound A while being heated at atemperature of 80° C. After completion of the addition, the resultingmixture was heated up to 130° C. and refluxed for 3 hours therebyobtaining an ultraviolet absorbing material in the form of a solution(coating liquid).

Preparation of Ultraviolet Absorbing Transparent Substrate

The ultraviolet absorbing material thus obtained was spray-coated over aglass substrate and disposed still at room temperature for 20 minutes,followed by heating at a temperature of 200° C. for 20 minutes therebyproducing an ultraviolet absorbing glass having an ultraviolet absorbinglayer with a thickness of 17 μm. A grid test was conducted for theresulting ultraviolet absorbing glass and 50% of peel-off was observed.

A portion of the ultraviolet absorbing layer was scraped out andsubjected to ¹³C-NMR analysis. It was observed that there was a peak ofcarbonyl (about 173 ppm) derived from the amide bond. ²⁹Si-NMR analysisalso revealed the existence of the Si—O bond.

After the resulting ultraviolet absorbing glass was extracted in boiledacetone for 24 hours, about 3% of change in ultraviolet absorbing powerwas observed in accordance with the measurement using theabove-described mathematical formula (1). From this measurement, it wasfound that the ultraviolet absorber was bonded to the resin throughaminosilane.

FIG. 6 shows the ultraviolet visible absorbing spectrum of theultraviolet absorbing glass. As apparent form FIG. 6, the glasscompletely shielded ultraviolets of less than 400 nm. The result of thepencil hardness test stipulated by JIS K5400 was 2H. The ultravioletabsorbing glass was left in a sunshine weather meter for 1000 hours andthe change rate in ultraviolet absorbing power was still less than 2%.

EXAMPLE 10

Preparation of Ultraviolet Absorbing Multi-layer Glass

A multi-layer glass was prepared in a conventional manner by using theultraviolet absorbing glass obtained in Example 9 and a commercial sodalime glass. There were used an aluminum spacer, a corner key, a butylrubber, a drying agent and polysulfide all of which are manufactured byTeipa Chemical Industry Co., Ltd. The resulting multi-layer glass wassuperior in heat resistance and capable of perfectly shieldingultraviolets over an extended period of time.

EXAMPLE 11

A silicone resin (APZ-7705, manufactured by Nippon Unicar Co., Ltd.) wasspray-coated over the ultraviolet absorbing layer of the ultravioletabsorbing glass obtained in Example 9 and dried at a temperature of 100°C. for 20 minutes thereby forming a protection layer having a thicknessof 2 μm.

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the protection layer by sputtering at a substratetemperature of 250° C. to form a transparent electrically conductivelayer having a layer thickness of about 3300 Å and an electricalresistance of 7.5 Ω/cm² thereby producing a transparent electricallyconductive substrate having ultraviolet absorbing capability. FIG. 6shows the spectral transmittance of the resulting transparentelectrically conductive substrate.

EXAMPLE 12

The ultraviolet absorbing material obtained in Example 9 wasspray-coated over a unwoven textile of red color and disposed still atroom temperature for 20 minutes, followed by heating at a temperature of200° C. for 20 minutes thereby obtaining an ultraviolet absorbing resinplate having an ultraviolet absorbing layer with a thickness of 17 μm.The resulting resin plate was left under radiation of ultraviolet rayand observed to be less in discoloration than a plate devoid of thecoating.

EXAMPLE 13

Preparation of Ultraviolet Absorbing Material

17.7 grams of silicone varnish manufactured by Okitsumo Co., Ltd. underthe trade name of XO-7931-CLEAR and 3 grams of3-aminopropyltriethoxysilane were dissolved in 35 grams of xylene andadded gradually with 5 grams of Compound A while being heated at atemperature of 80° C. After completion of the addition, the resultingmixture was heated up to 130° C. and refluxed for 3 hours, followed bybeing allowed to cool down, thereby obtaining an ultraviolet absorbingmaterial in the form of a solution (coating liquid).

Preparation of Ultraviolet Absorbing Transparent Substrate

The ultraviolet absorbing material thus obtained was spray-coated over aglass substrate and disposed still at room temperature for 20 minutes,followed by heating at a temperature of 200° C. for 20 minutes therebyproducing an ultraviolet absorbing glass having an ultraviolet absorbinglayer with a thickness of 17 μm. Unlike Example 9, a grid test revealedno peeling-off.

A portion of the ultraviolet absorbing layer was scraped out andsubjected to ¹³C-NMR analysis. It was observed that there was a peak ofcarbonyl (about 173 ppm) derived from the amide bond. ²⁹Si-NMR analysisalso revealed the existence of the Si—O bond. FIG. 7 shows ultravioletvisible absorbing spectrum of the resulting glass plate. As apparentform FIG. 7, the glass was found to have a superior ultravioletshielding capability similar to that of Example 1. The ultravioletabsorbing glass performed a superior ultraviolet shielding capabilityover an extended period of time.

EXAMPLE 14

Preparation of Ultraviolet

A multi-layer glass was prepared in a conventional manner by using theultraviolet absorbing glass obtained in Example 13 and a commercial sodalime glass. There were used an aluminum spacer, a corner key, a butylrubber, a drying agent and polysulfide all of which are manufactured byTeipa Chemical Industry Co., Ltd. The resulting multi-layer glass wassuperior in heat resistance and capable of perfectly shieldingultraviolets over an extended period of time.

EXAMPLE 15

A silicone resin (APZ-7705, manufactured by Nippon Unicar Co., Ltd.) wasspray-coated over the ultraviolet absorbing layer of the ultravioletabsorbing glass obtained in Example 13 and dried at a temperature of100° C. for 20 minutes thereby forming a protection layer having athickness of 2 μm.

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the protection layer thus formed by sputtering at asubstrate temperature of 250° C. to form a transparent electricallyconductive layer having a layer thickness of about 3300 Å and anelectrical resistance of 7.5 Ω/cm² thereby producing a transparentelectrically conductive substrate having ultraviolet absorbingcapability. FIG. 7 shows the spectral transmittance of the transparentelectrically conductive substrate.

EXAMPLE 16

The ultraviolet absorbing material obtained in Example 13 wasspray-coated over a acrylic plate of red color and disposed still atroom temperature for 20 minutes, followed by heating at a temperature of200° C. for 20 minutes thereby obtaining an ultraviolet absorbing resinplate having an ultraviolet absorbing layer with a thickness of 17 μm.The resulting resin plate was left under radiation of ultraviolet rayand observed to be less in discoloration than a plate devoid of thecoating.

EXAMPLE 17

Preparation of Ultraviolet Absorbing Material

17.7 grams of silicone varnish manufactured by Okitsumo Co., Ltd. underthe trade name of XO-7931-CLEAR and 3 grams of3-aminopropyltriethoxysilane were dissolved in 35 grams of xylene andadded gradually with 5 grams of Compound A while being heated at atemperature of 80° C. After completion of the addition, the resultingmixture was heated up to 130° C. and refluxed for 3 hours. Then themixture was allowed to cool down and added with 16 grams of3-glycidoxypropyltrimethoxysilane and 8 grams of colloidal silicadispersions manufactured by Nissan Kagaku Co., Ltd. under the trade nameof “MIBK-ST” thereby obtaining an ultraviolet absorbing material in theform of a solution (coating liquid).

Preparation of Ultraviolet Absorbing Transparent Substrate

The ultraviolet absorbing material thus obtained was spray-coated over aglass substrate and disposed still at room temperature for 20 minutes,followed by heating at a temperature of 200° C. for 20 minutes therebyproducing an ultraviolet absorbing glass having an ultraviolet absorbinglayer with a thickness of 17 μm. The result of a pencil hardness test inaccordance with JIS K 5400 was 4H.

A portion of the ultraviolet absorbing layer was scraped out andsubjected to ¹³C-NMR analysis. It was observed that there was a peak ofcarbonyl (about 173 ppm) derived from the amide bond. ²⁹Si-NMR analysisalso revealed the existence of the Si—O bond. FIG. 8 shows theultraviolet visible absorbing spectrum of the resulting glass plate. Asapparent form FIG. 8, the glass was found to have a superior ultravioletshielding capability similar to that of Example 1. The ultravioletabsorbing glass performed a superior ultraviolet shielding capabilityover an extended period of time.

EXAMPLE 18

Preparation of Ultraviolet Absorbing Multi-layer Glass

A multi-layer glass was prepared in a conventional manner by using theultraviolet absorbing glass obtained in Example 17 and a commercial sodalime glass. There were used an aluminum spacer, a corner key, a butylrubber, a drying agent and polysulfide all of which are manufactured byTeipa Chemical Industry Co., Ltd. The resulting multi-layer glass wassuperior in heat resistance and capable of perfectly shieldingultraviolets over an extended period of time.

EXAMPLE 19

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the ultraviolet absorbing glass prepared in Example 17by sputtering at a substrate temperature of 250° C. to form atransparent electrically conductive layer having a layer thickness ofabout 3300 Å and an electrical resistance of 7.5 Ω/cm² thereby producinga transparent electrically conductive substrate having ultravioletabsorbing capability. FIG. 8 shows the spectral transmittance of thetransparent electrically conductive substrate.

EXAMPLE 20

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the ultraviolet absorbing glass of prepared in Example17 by sputtering at a substrate temperature of 250° C. to form atransparent electrically conductive layer having a layer thickness ofabout 3300 Å and an electrical resistance of 7.5 Ω/cm² thereby producinga transparent electrically conductive substrate having ultravioletabsorbing capability. The ultraviolet visible absorbing spectrum of theresulting substrate was measured and found to have a superiorultraviolet shielding capability similarly to that of Example 1.

EXAMPLE 21

The ultraviolet absorbing material obtained in Example 17 wasspray-coated over a polycarbonate of red color and disposed still atroom temperature for 20 minutes, followed by heating at a temperature of200° C. for 20 minutes thereby obtaining an ultraviolet absorbing resinplate having an ultraviolet absorbing layer with a thickness of 17 μm.The resulting resin plate was left under radiation of ultraviolet rayand found to be less in discoloration than a plate devoid of thecoating.

EXAMPLE 22

Preparation of Solution of Epoxysilane Copolymer

200 grams of 3-glycidoxypropylmethoxysilane was dissolved in 75 gramsxylene and added gradually with 4 ml boron trifluoride diethylehtercomplex at room temperature. The resulting mixture was stirred for 4hours and then subjected to ring-opening polymerization therebypreparing a epoxysilane copolymer solution. The resulting polymer was3,300 Mw in molecular weight by polystylene conversion.

Preparation of Ultraviolet Absorbing Coating Liquid

17.7 grams of silicone varnish manufactured by Okitsumo Co., Ltd. underthe trade name of XO-7931-CLEAR and 3 grams of3-aminopropyltriethoxysilane were dissolved in 29 grams of xylene andadded gradually with 5 grams of Compound A while being heated at atemperature of 80° C. After completion of the addition, the resultingmixture was heated up to 130° C. and refluxed for 3 hours. The mixturewas allowed to cool down and added with 22 grams of the epoxysilanecopolymer solution obtained above thereby obtaining an ultravioletabsorbing material in the form of a solution (coating liquid).

Preparation of Ultraviolet Absorbing Transparent Substrate

The ultraviolet absorbing material thus obtained was spray-coated over aglass substrate and disposed still at room temperature for 20 minutes,followed by heating at a temperature of 150° C. for 30 minutes therebyproducing an ultraviolet absorbing glass having an ultraviolet absorbinglayer with a thickness of 15 μm. The result of a pencil hardness test inaccordance with JIS K 5400 was 6H.

A portion of the ultraviolet absorbing layer was scraped out andsubjected to ¹³C-NMR analysis. It was observed that there was a peak ofcarbonyl (about 173 ppm) derived from the amide bond. ²⁹Si-NMR analysisalso revealed the existence of the Si—O bond. FIG. 9 shows theultraviolet visible absorbing spectrum of the resulting glass plate. Asapparent form FIG. 9, the glass was found to have a superior ultravioletshielding capability similar to that of Example 1. The ultravioletabsorbing glass performed a superior ultraviolet shielding capabilityover an extended period of time.

EXAMPLE 23

Preparation of Ultraviolet Absorbing Multi-layer Glass

A multi-layer glass was prepared in a conventional manner by using theultraviolet absorbing glass obtained in Example 22 and a commercial sodalime glass. There were used an aluminum spacer, a corner key, a butylrubber, a drying agent and polysulfide all of which are manufactured byTeipa Chemical Industry Co., Ltd. The resulting multi-layer glass wassuperior in heat resistance and capable of perfectly shieldingultraviolets over an extended period of time.

EXAMPLE 24

A silicone resin (APZ-7705, manufactured by Nippon Unicar Co., Ltd.) wasspray-coated over the ultraviolet absorbing layer of the ultravioletabsorbing glass obtained in Example 22 and dried at a temperature of100° C. for 20 minutes thereby forming a protection layer having athickness of 2 μm.

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the protection layer thus formed by sputtering at asubstrate temperature of 250° C. to form a transparent electricallyconductive layer having a layer thickness of about 3300 Å and anelectrical resistance of 7.5 Ω/cm² thereby producing a transparentelectrically conductive substrate having ultraviolet absorbingcapability. FIG. 9 shows the spectral transmittance of the transparentelectrically conductive substrate.

EXAMPLE 25

The ultraviolet absorbing material obtained in Example 22 wasspray-coated over a plywood of red color and disposed still at roomtemperature for 20 minutes, followed by heating at a temperature of 200°C. for 20 minutes thereby obtaining an ultraviolet absorbing resin platehaving an overcoated ultraviolet absorbing layer with a thickness of 17μm. The resulting resin plate was left under radiation of ultravioletray and observed to be less in discoloration than a plate devoid ofcoating.

EXAMPLE 26

The ultraviolet absorbing material (coating liquid) prepared in Example22 was further added with 8 gram colloidal silica dispersionsmanufactured by Nissan Kagaku Co., Ltd. under the trade name of“MIBK-ST” thereby obtaining an ultraviolet absorbing material (newcoating liquid).

The new coating liquid was spray-coated over a glass substrate anddisposed still at room temperature for 20 minutes, followed by heatingat a temperature of 150° C. for 30 minutes thereby obtaining a glassplate having an ultraviolet absorbing layer with a thickness of 15 μm.The resulting substrate was measured for ultraviolet visible absorbingspectrum and found to have superior ultraviolet shielding capabilitysimilarly to that of Example 1.

EXAMPLE 27

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the ultraviolet absorbing glass prepared in Example 26by sputtering at a substrate temperature of 250° C. to form atransparent electrically conductive layer having a layer thickness ofabout 3300 Å and an electrical resistance of 7.5 Ω/cm² thereby producinga transparent electrically conductive substrate having ultravioletabsorbing capability. The ultraviolet visible absorbing spectrum of theresulting substrate was measured and found to have a superiorultraviolet shielding capability similarly to that of Example 1.

EXAMPLE 28

Preparation of Ultraviolet Absorbing Material

3 grams of 3-aminopropyltriethoxysilane and 11 grams of the epoxysilanecopolymer solution prepared in Example 6 were dissolved in 32 grams ofxylene and added gradually with 5 grams of Compound A while being heatedat a temperature of 80° C. After completion of the addition, theresulting mixture was heated up to 130° C. and refluxed for 3 hoursthereby obtaining an ultraviolet absorbing material (coating liquid).

Preparation of Ultraviolet Absorbing Transparent Substrate

The ultraviolet absorbing material thus obtained was spray-coated over aglass substrate and disposed still at room temperature for 20 minutes,followed by heating at a temperature of 150° C. for 30 minutes therebyproducing an ultraviolet absorbing glass having an ultraviolet absorbinglayer with a thickness of 15 μm. The result of a pencil hardness test inaccordance with JIS K 5400 was 5H.

A portion of the ultraviolet absorbing layer was scraped out andsubjected to ¹³C-NMR analysis. It was observed that there was a peak ofcarbonyl (about 173 ppm) derived from the amide bond. ²⁹Si-NMR analysisalso revealed the existence of the Si—O bond. FIG. 10 shows theultraviolet visible absorbing spectrum of the resulting glass plate. Asapparent form FIG. 10, the glass was found to have a superiorultraviolet shielding capability similarly to that of Example 1. Theultraviolet absorbing glass performed superior ultraviolet shieldingcapability over an extended period of time.

EXAMPLE 29

Preparation of Ultraviolet Absorbing Multi-layer Glass

A multi-layer glass was prepared in a conventional manner by using theultraviolet absorbing glass obtained in Example 28 and a commercial sodalime glass. There were used an aluminum spacer, a corner key, a butylrubber, a drying agent and polysulfide all of which are manufactured byTeipa Chemical Industry Co., Ltd. The resulting multi-layer glass wassuperior in heat resistance and capable of perfectly shieldingultraviolets over an extended period of time.

EXAMPLE 30

A silicone resin (APZ-7705, manufactured by Nippon Unicar Co., Ltd.) wasspray-coated over the ultraviolet absorbing layer of the ultravioletabsorbing glass obtained in Example 28 and dried at a temperature of100° C. for 20 minutes thereby forming a protection layer having athickness of 2 μm.

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the protection layer thus formed by sputtering at asubstrate temperature of 250° C. to form a transparent electricallyconductive layer having a layer thickness of about 3300 Å and anelectrical resistance of 7.5 Ω/cm² thereby producing a transparentelectrically conductive substrate having ultraviolet absorbingcapability. FIG. 10 shows the spectral transmittance of the transparentelectrically conductive substrate.

EXAMPLE 31

The ultraviolet absorbing material obtained in Example 28 wasspray-coated over a ceramic of red color and disposed still at roomtemperature for 20 minutes, followed by heating at a temperature of 200°C. for 20 minutes thereby obtaining an ultraviolet absorbing resin platehaving an ultraviolet absorbing layer with a thickness of 17 μm. Theresulting resin plate was left under radiation of ultraviolet ray andobserved to be less in discoloration than a plate devoid of coating.

EXAMPLE 32

The ultraviolet absorbing material (coating liquid) prepared in Example28 was further added with 8 gram colloidal silica dispersionsmanufactured by Nissan Kagaku Co., Ltd. under the trade name of“MIBK-ST” thereby obtaining an ultraviolet absorbing material (newcoating liquid).

The new coating liquid was spray-coated over a glass substrate anddisposed still at room temperature for 20 minutes, followed by heatingat a temperature of 150° C. for 30 minutes thereby obtaining a glassplate having an ultraviolet absorbing layer with a thickness of 15 μm.The ultraviolet visible absorbing spectrum of the resulting substratewas measured and found to have superior ultraviolet shielding capabilitysimilarly to that of Example 1.

EXAMPLE 33

Preparation of Ultraviolet Absorbing Transparent Electrically ConductiveSubstrate

ITO was formed on the ultraviolet absorbing glass prepared in Example 32by sputtering at a substrate temperature of 250° C. to form atransparent electrically conductive layer having a layer thickness ofabout 3300 Å and an electrical resistance of 7.5 Ω/cm² thereby producinga transparent electrically conductive substrate having ultravioletabsorbing capability. The ultraviolet visible absorbing spectrum of theresulting substrate was measured and found to have a superiorultraviolet shielding capability similarly to that of Example 1.

COMPARATIVE EXAMPLE 1

22.2 grams of silicone varnish manufactured by Okitsumo Co., Ltd. underthe trade name of XO-7931 -CLEAR was added with 10 grams of octyl3-(5-chloro-2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenpropanate manufactured by Chiba-Geigy Co., Ltd. under the trade name ofTINUVIN 109 and then with 20 μl di-n-butyltin dilaurate, followed bydilution with 20 ml of dimethyl formamide (DMF). The resulting mixturewas spray-coated over a glass substrate. The resulting product was driedon a hot plate at 60° C. for 15 minutes and cured by heating in an ovenat 200° C. for one hour thereby obtaining an ultraviolet absorbing glasshaving an ultraviolet absorbing layer about 20 μm. The resultingultraviolet absorbing glass became whitely turbid due to theprecipitation of the ultraviolet absorber.

COMPARATIVE EXAMPLE 2

22.2 grams of silicone varnish manufactured by Okitsumo Co., Ltd. underthe trade name of XO-7931-CLEAR was added with 2.2 grams of octyl3-(5-chloro-2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenpropanate manufactured by Chiba-Geigy Co., Ltd. under the trade name ofTINUVIN 109 and then with 20 μl di-n-butyltin dilaurate, followed bydilution with 20 ml of dimethyl formamide (DMF). The resulting mixturewas spray-coated over a glass substrate. The resulting product was driedon a hot plate at 60° C. for 15 minutes and cured by heating in an ovenat 200° C. for one hour thereby obtaining an ultraviolet absorbing glasshaving an ultraviolet absorbing layer about 15 μm. The resultingultraviolet absorbing glass did not become whitely turbid but wereinsufficient in ultraviolet shielding capability.

The resulting ultraviolet absorbing glass was subjected to extraction inboiled acetone similarly to that of Example 9. It was found that therewas 48% decrease in weight and 95% change rate in ultraviolet absorbingcapability and that most of the ultraviolet absorber was eluted.Furthermore, the glass was left in a sunshine weather meter for 1000hours. There was found 50% change rate in ultraviolet absorbingcapability and thus reduced ultraviolet shielding capability.

COMPARATIVE EXAMPLE 3

Ultra-fine ZnO particle dispersion coatings manufactured by Resino ColorIndustry Co., Ltd. under the trade name of UV-S-400 was dip-coated overa glass substrate and cured by heating at 200° C. for 20 minutes therebyforming an ultraviolet absorbing layer having a thickness of 2 μm. Amethylene chloride solution of polyether sulfone manufactured by ICICo., Ltd. under the trade name of “VICTREX” PES 4100 P was spin-coatedover the ultraviolet absorbing layer thus formed thereby forming apolymer layer of about 2 μm in thickness.

On the polymer layer was further coated the silicone varnish used inExample 2 to form an ultraviolet absorbing layer of 15 μm in thickness.

Polyimide varnish manufactured by Nissan Chemical Industries Co., Ltd.under the trade name of RN-812 was then spin-coated over the ultravioletabsorbing layer thus formed. The resulting product was cured by heatingin an oven at a temperature of 200° C. for 30 minutes after the solventwas dried off at a hot plate at a temperature of 60° C. thereby formingan overcoat layer of 2 μm. Then, ITO was formed over the overcoat layerby sputtering at a substrate temperature of not higher than 250° C.thereby obtaining a transparent electrically conductive substrate havinga transparent electrically conductive ultraviolet shielding layer with alayer thickness of 2050 Å and a surface resistance of 9.5 Ω/cm². FIG. 11shows the spectral transmittance of the transparent electricallyconductive substrate.

What is claimed is:
 1. An ultraviolet absorbing plate produced byproviding on a substrate an ultraviolet absorbing layer formed from anultraviolet absorbing material having an amide bond and an Si—O bond,wherein said ultraviolet absorbing material comprises a reaction productof (a) an aminosilane compound of formula (1) or a hydrolysate thereofwith (b) an ultraviolet absorber having in its molecules a carboxylgroup so as to form an amide bond derived from the aminosilane compoundor a hydrolysate thereof, said formula (1) being represented by

 wherein R¹ is a C₁-C₁₀ alkylene group or a divalent group of theformula —(CH2)_(m)—NH— in which m is an integer of 1-4, R² are the sameor different and each is selected from the group consisting of ahydrogen atom, a hydroxyl group, a halogen atom, a C₁-C₁₀ alkyl groupand a C₁-C₁₀ alkoxy group, provided that at least one of R² is an alkoxygroup, and n is an integer of 0 or greater.
 2. An ultraviolet absorbingplate according to claim 1 wherein the reaction of said aminosilanecompound or a hydrolysate thereof with said ultraviolet absorber havingin its molecules an carboxyl group is conducted in the presence of asilicone resin or is conducted and thereafter added with a siliconeresin after completion of the reaction.
 3. An ultraviolet absorbingplate according to claim 1 wherein said ultraviolet absorbing materialis produced by reacting (a) an aminosilane compound of formula (1) or ahydrolysate thereof with (b) an ultraviolet absorber having in itsmolecules a carboxyl group in the presence of a silane compound havingin its molecules an epoxy group and/or a colloidal silica so as to forman amide bond derived from the aminosilane compound or a hydrolysatethereof or by adding a silane compound having in its molecules an epoxygroup and/or a colloidal silica to a reaction product obtained byreacting (a) an aminosilane compound of formula (1) or a hydrolysatethereof with (b) an ultraviolet absorber having in its molecules acarboxyl group so as to form an amide bond derived from the aminosilanecompound or the derivative thereof, said formula (1) being representedby

 wherein R¹ is a C₁-C₁₀ alkylene group or a divalent group of theformula —(CH₂)m—NH— in which m is an integer of 1-4, R² are the same ordifferent and each is selected from the group consisting of a hydrogenatom, a hydroxyl group, a halogen atom, a C₁-C₁₀ alkyl group and aC₁-C₁₀ alkoxy group provided that at least one of R² is an alkoxy group,and n is an integer of 0 or greater.
 4. An ultraviolet absorbing plateaccording to claim 1 wherein said substrate and said ultravioletabsorbing layer are transparent.
 5. An ultraviolet absorbing plateaccording to claim 1 wherein said substrate comprises a plurality oftransparent substrate laminated one after another and one or more saidultraviolet absorbing layer disposed therebetween.
 6. An ultravioletabsorbing plate according to claim 1 which has an overcoat layer on saidultraviolet absorbing layer.
 7. An ultraviolet absorbing plate accordingto claim 1 which has a transparent electrically conductive layer on theside where said ultraviolet absorbing layer is disposed.
 8. Anultraviolet absorbing plate according to claim 7 which has an overcoatlayer between said ultraviolet absorbing layer and said transparentelectrically conductive layer.
 9. The ultraviolet absorbing plateaccording to claim 1, wherein the ultraviolet absorber is abenzotriazole molecule or a benzophenone molecule.
 10. An ultravioletabsorbing material comprising a reaction product of (a) an aminosilanecompound of formula (I) or a hydrolysate thereof with (b) an ultravioletabsorber having in its molecules a carboxyl group so as to form an amidebond derived from the aminosilane compound or a hydrolysate thereof,said formula (1) being represented by

 wherein R¹ is a C₁-C₁₀ alkylene group or a divalent group of theformula —(CH₂)m—NH— in which m is an integer of 1-4, R² are the same ordifferent and each is selected from the group consisting of a hydrogenatom, a hydroxyl group, a halogen atom, a C₁-C₁₀ alkyl group and aC₁-C₁₀ alkoxy group provided that at least one of R² is an alkoxy group,and n is an integer of 0 or greater.
 11. The ultraviolet absorbingmaterial according to claim 10, wherein the ultraviolet absorber is abenzotriazole molecule or a benzophenone molecule.